1
1FTIR spec oscopic semi-quan i ica ion o i on phases: a new
2me hod o e alua e he P o ec ion Abili y Index (PAI) o
3a chaeological a e ac s co osion sys ems
4Ma co Vene anda1*, Julene A amendia1, Ludo ic Bello -Gu le 2, Philippe
5Colomban2, Kepa Cas o1, Juan Manuel Mada iaga1,3
61 Depa men o Analy ical Chemis y, Facul y o Science and Technology, Uni e si y o he
7Basque Coun y UPV/EHU, P.O. Box 644, 48080 Bilbao, Basque Coun y, Spain.
8[email p o ec ed]
92 So bonne Uni e si és, UPMC Uni e si é Pa is 6, MONARIS ‘de la Molécule aux Nano-
10 obje s: Réac i i é, In e ac ions e Spec oscopies’, UMR 8233, CNRS, 4 Place Jussieu, 75005,
11 Pa is, F ance
12 3 Unesco Chai o Cul u al Landscapes and He i age, Uni e si y o he Basque Coun y
13 (UPV/EHU), P.O. Box 450, 01080, Vi o ia-Gas eiz, Spain
14 Abs ac :
15 This s udy p oposes an inno a i e app oach o semi-quan i y he main i on co osion
16 phases ound in co osion sys ems o a chaeological a e ac s. This me hod is based on
17 he ea men o Fou ie T ans o m In a ed Spec oscopy (FTIR) da a using a
18 homemade spec a decomposi ion so wa e (PALME). I s applica ion was i s es ed on
19 mix u es o pu e i on co osion s anda ds. A e op imiza ion, i was used o s udy eal
20 a chaeological samples and e alua e he s abili y o hei co osion sys em.
21 Conside ing ha eliable and epe i i e esul s we e eached using ex emely small
22 quan i ies o ma e ial, his me hod can be pa icula ly sui able o he s udy o i on-
23 based objec s o cul u al in e es .
24 Keywo ds: I on co osion; Semi-quan i ica ion; Fou ie T ans o m In a ed
25 Spec oscopy; PALME so wa e; Spec a decomposi ion; A chaeological a e ac s;
26 1 In oduc ion:
27 The indispensable condi ion o ensu e p ope conse a ion o ancien i on a e ac s is o
28 each a s a e o chemical and physical balance wi h he en i onmen in which hey a e
29 p ese ed [1].
This is he accep ed manusc ip o he a icle ha appea ed in inal o m in Co osion Science 133 : 68-77 (2018), which has been
published in inal o m a h ps://doi.o g/10.1016/j.co sci.2018.01.016. © 2018 Else ie unde CC BY-NC-ND license (h p://
c ea i ecommons.o g/licenses/by-nc-nd/4.0/)
2
1In his sense, he eco e y o i ons om a chaeological si es only akes place when hei
2ma ix eaches he equilib ium wi h he soil, main aining i h oughou he bu ial ime.
3Howe e , his delica e balance su e s a c i ical dis up ion du ing a chaeological
4exca a ion. In ac , a e ac s eco e y exposes hem o a comple ely di e en
5en i onmen , esul ing o en in he ac i a ion o many deg ada ion pa hways [2].
6The e o e, conse a o s mus ac p omp ly in he la e s ages o a chaeological
7exca a ion wi h he pu pose o achie ing, h ough speci ic conse a ion ea men s, a
8 enewed equilib ium wi h he new en i onmen al con ex [3,4].
9In his ligh , he wo k o conse a o s can be s ongly bene i ed om analy ical s udies.
10 In he ea ly s age, he molecula analysis o i on a e ac s enables he iden i ica ion o
11 he co osion phases de eloped du ing he bu ial ime. Those quali a i e da a a e
12 ex emely impo an o conse a o s, helping hem o iden i y he eal p ese a ion s a e
13 o he analysed objec . This is because each i on co osion phase has a di e en
14 in luence on he conse a ion o a e ac s. Wi h ega ds o a chaeological i on a e ac s
15 esumed om oxic en i onmen s, he co osion sys em is gene ally mainly composed o
16 magne i e (Fe3O4), goe hi e (α-FeOOH), lepidoc oci e (γ-FeOOH) and akaganei e (β-
17 FeOOH). In his con ex , is i well known ha magne i e and goe hi e a e s able
18 compounds ha help he p ese a ion o indings, whe eas lepidoc oci e and akaganei e
19 can be conside ed as deg ada ion accele a o s, as seen in he li e a u e [5-7].
20 In addi ion o quali a i e analysis, u he use ul in o ma ion can be ob ained by
21 de e mining he ela i e concen a ion (quan i a i e o semi-quan i a i e analysis) o
22 each i on phase composing he co osion sys em. Fo example, he quan i a i e analysis
23 o agmen s ha , one a e he o he , a e emo ed by conse a o s du ing he
24 conse a ion wo k helps o iden i y he in-dep h dis ibu ion o he eac i e deg ada ion
25 p oduc s and o cha ac e ize he eac i i y o he whole co osion sys em [8]. Such
26 app oaches we e also de eloped in he con ex o a mosphe ic co osion in which he
27 quan i ica ion o i on phases was been o desc ibe he s abili y o he co osion laye s
28 [9,10].
29 The quan i a i e analysis o i on co osion can also ind eliable applica ions in he
30 s ages ollowing he conse a ion wo ks. In he sho e m, i can be used o con ol
31 whe he conse a ion ea men s we e able o s abilize he eac i e co osion
3
1phases[11]. In he long e m, i can also be used o iden i y any new co osion p ocesses
2 ha may be en ailed by he in e ac ion be ween he objec and he s o age/exhibi ion
3en i onmen al condi ions [12,13].
4In his con ex , molecula analy ical echniques such as X-Ray Di ac ion (XRD)
5[14,15] and Mossbaue spec oscopy [16,17] ha e been ex ensi ely used wi h he
6speci ic pu pose o de e mining he ela i e concen a ion o he phases ha compose
7 he i on co osion sys ems.
8Mo e o e , Raman spec oscopy is acqui ing a s eadily inc easing impo ance in s udies
9 ela ed o cul u al he i age ma e ials due o i s e sa ili y and capabili y o collec ing
10 molecula da a in a non-in usi e way[18].
11 Conside ing ha he in ensi y o Raman signals a e p opo ional o he concen a ion,
12 he mos used quan i ica ion me hod is he one based on he use o ex e nal calib a ion
13 cu es [19-21]. To a oid he use o calib a ion cu es o each analysed compound and
14 hei mixing, an app oach using spec al decomposi ion in a linea combina ion o
15 e e ence spec a was p oposed o s udying a mosphe ic co osion o medie al i on
16 [10]. To go u he han using poin analyses he co osion he e ogenei ies we e aken
17 in o accoun using he au oma ed ea men o Raman maps o e he co osion sys em.
18 This app oach was also applied o he diagnos ic o sel -wea he ing s eel a mosphe ic
19 co osion o con empo a y wo k o A [22].
20 Howe e , i mus be poin ed ou ha Raman spec oscopy is poo ly sui able o he
21 s udy o ma e ials ea u ing high au o- luo escence emissions. In hese cases, he use o
22 Fou ie T ans o m In a ed Spec oscopy (FTIR) is mo e indica ed, since i a oids any
23 p oblem ela ed o he au o- luo escence o he sample. Mo eo e , wo king wi h
24 powde ed samples, FTIR sys ems also ensu e a be e accu acy and epea abili y o he
25 esul s o e he sample he e ogenei ies by sampling he whole co osion sys em [23].
26 E en hough FTIR sys ems ha e been success ully applied o he quan i ica ion o
27 se e al kind o liquid [24,25] and solid [26,27] samples, only a ew wo ks desc ibe he
28 use o his spec oscopic echnique o he quan i ica ion o i on phases [28, 29].
29 Conside ing ha his analy ical app oach has ne e been applied in he ield o cul u al
30 he i age cha ac e iza ion, he main objec i e o he p esen wo k was o e alua e i FTIR
4
1spec oscopy can be used as an al e na i e echnique o semi-quan i y he main
2co osion phases o i on a chaeological a e ac s. Fo his pu pose, a dedica ed so wa e
3(PALME) designed by he LADIR g oup (now MONARIS, Pie e and Ma ie Cu ie
4Uni e si y, F ance) was employed o pe o m he decomposi ion o FTIR spec a.
5A e wa ds, he p oposed p ocedu e was also used o assess whe he i can be used o
6 eliably assess he s abili y o eal us samples coming om a chaeological a e ac s. In
7 his ega ds, he s abili y assessmen has been inspi ed by he p o ec ion abili y index
8(PAI index), p oposed o he i s ime by Yamashi a e al. [30] and subsequen ly
9adjus ed by Dillmann e al. [7] o he analysis o us laye s co e ing ancien i on
10 objec s exposed o a mosphe ic co osion.
11 The main ad an age ob ained om PAI index calcula ion consis s in helping
12 conse a o s on p edic ing he co osion beha iou o i on a e ac s a e hei eco e y
13 om he a chaeological si e. Thus, objec s p o iding high s abili y alues can be ea ed
14 and s o ed by ollowing ou ine p o ocols, whe eas uns able a e ac s equi e a ge ed
15 ea men s in o de o p e en he onse o pos -exca a ion deg ada ion p ocesses. In his
16 con ex , i is impo an o cla i y ha he semi-quan i ica ion o i on phases in ol es he
17 sampling / p ocessing o co osion ma e ial. Howe e , his aspec does no ep esen a
18 ema kable issue since hick co osion sys ems a e gene ally emo ed / hinned in o de
19 o eco e he o iginal shape o he a e ac s [31].
20 2 Expe imen al me hods and es s
21 2.1 Samples p epa a ion
22 This wo k was based on he analysis o bo h, s anda d mix u es and a chaeological us
23 samples. In he i s case, pu e magne i e, lepidoc oci e and goe hi e i on phases ( om
24 Sigma-Ald ich co p. S Luis, USA) we e kindly p o ided by D. Ne om he LAPA
25 g oup (NIMBE UMR3685 CEA/CNRS, F ance). On he o he hand, pu e akaganei e
26 was syn hesized using he me hod desc ibed by Regue e al. [32]. The syn hesis me hod
27 in ol ed he hyd olysis o a 0.1 M e ic chlo ide solu ion (FeCl3 • 6H2O) by hea ing 2
28 li e s o he solu ion a 70 °C du ing 48 h.
29 On he one hand, 10 s anda d mix u es we e p epa ed by mixing i on oxide and
30 oxyhyd oxide s anda ds a di e en p opo ions. Conside ing ha FTIR spec oscopy
5
1needs a small pa icle size (1-2 μm) o a oid any dis o ion phenomena, an aga e mo a
2was used o he g inding and he homogeniza ion o all samples. The ela i e weigh o
3each i on phase in he mix u es was moni o ed by using an analy ical balance (AE200,
4Me le ) wi h an accu acy o 0.0001 g.
5On he o he hand, eal samples we e collec ed om i on a e ac s exca a ed in he
6Roman a chaeological si e o Fo ua (Spain) [33]. This Roman se lemen , disco e ed in
71982, s ands jus ew kilome es inland om he Bay o Biscay. In he a chaeological
8exca a ions se e al objec s we e disco e ed, including i e i on-based nails da ed back
9be ween he 2nd and he 4 h cen u y A.D (see Figu e SM1 in supplemen a y ma e ial).
10 Since hei eco e y, all a e ac s ha e been cons an ly kep in a con olled en i onmen
11 oom ( empe a u e and ela i e humidi y o 20 ± 2 °C and 65 ± 2% espec i ely)
12 wi hou he implemen a ion o u he conse a ion ea men s. To minimize pos -
13 exca a ion co osion phenomena, each nail had been s o ed in he me ic boxes equipped
14 wi h desiccan silica gel beads ha ensu e humidi y le els below 10% ela i e humidi y.
15 In he ame o his s udy, one us mic o-sample was collec ed om each o he i e
16 nails. The sampling, ca ied ou wi h he collabo a ion o he conse a o s o he
17 A chaeological Museum o Bizkaia, was pe o med a e cleaning he ou e us laye
18 om impu i ies (e.g. ea h, clays and o ganic ma e ial) deposi ed on i s su ace du ing
19 he bu ial ime. In his way, he possible in e e ences p opo ioned by ex aneous
20 ma e ials du ing he analy ical cha ac e iza ion o he i on co osion we e minimized.
21 The collec ed samples we e inally analysed o semi-quan i y he main i on phases and
22 e alua e hei s abili y h ough he p o ec i e abili y index calcula ion.
23 2.2 FTIR sys ems
24 Fo he de elopmen o his wo k wo FTIR sys ems we e used. On he one hand, a
25 Jasco 6300 sys em, ope a ing in ansmi ance, di use e lec ion (DRIFT, Jasco DR
26 PR0410M) and ATR (diamond c ys al wi h a ZnSe ocusing lens, PIKE Mi acle™)
27 modes, was used wi h he aim o checking wha con igu a ion p o ided he mos
28 eliable esul s. The ins umen is equipped wi h a Ge on KB beamspli e , a Michelson
29 in e e ome e and a DLaTGS de ec o wi h Pel ie empe a u e con ol. Analysis we e
30 pe o med in he middle in a ed egion ( om 4000 o 400 cm-1) eco ding 64 scans a 4
31 cm-1 spec al esolu ion.
6
1To collec ATR spec a, a small po ion o homogenized sample (a ound 0.05 g) was
2placed in he mic osample holde , i mly clamped agains he ATR c ys al and analysed
3in i s pu e o m.
4On he o he side, KB -ma ix pelle s we e made o ca y ou ansmi ance analysis. To
5p epa e he pelle s, 0.5 mg o sample was mixed wi h 170 mg o d y KB (>99% FTIR
6g ade, Sigma-Ald ich), milled in an aga e mo a and p essed unde 10 ons (C ushIR,
7PIKE echnologies) o 8 minu es.
8Fo DRIFT analysis, he mic osample holde was illed wi h a powde mix u e
9composed o 10% (w/w) sample and 90% (w/w) KB . This dilu ion a io ensu ed ha ing
10 a lowe specula componen on he su ace o he sample inc easing he con ibu ion o
11 he di use e lec ance componen [23].
12 In a second s ep, he esul s ob ained by he use o he abo e desc ibed labo a o y
13 ins umen s we e compa ed wi h hose o a po able FTIR. The aim was o e i y i he
14 p oposed semi-quan i ica ion me hod could be applied o in-si u analysis. Fo his
15 pu pose, a compac po able Alpha FTIR spec ome e (B uke Op ics Inc., Ge many)
16 equipped wi h a Ge on KB beamspli e and a diamond ATR accesso y was used.
17 To compa e he esul s o he po able ins umen wi h hose ob ained by he labo a o y
18 one, he same measu emen pa ame e s we e used (64 acquisi ions a 4 cm−1 esolu ion
19 o e a spec al ange o 400–4000 cm−1, see abo e).
20 To imp o e he eliabili y o he p oposed me hod, he FTIR spec a ob ained om bo h
21 po able and labo a o y sys ems we e ea ed using he Opus 7.2 so wa e (B uke
22 Op ics, Ge many). Thus, CO2/H2O and noise co ec ions, spec a baseline adjus men
23 and inge p in egion selec ion we e pe o med.
24 2.3 PALME so wa e
25 A e comple ing he analysis o all samples by using bo h FTIR sys ems, he PALME
26 so wa e (P og am d'AnaLyse ib a ionnelle de spec es de MElanges à pa i de
27 spec es pu s) de eloped by he LADIR Labo a o y (now MONARIS, Pie e e Ma ie
28 Cu ie Uni e si y, F ance) was applied o semi-quan i y he de ec ed i on co osion
29 phases. This p og am was speci ically designed o ea spec a p o ided by ib a ional
30 spec oscopy echniques. PALME so wa e au oma ically pe o ms he semi-
7
1quan i ica ion o compounds mix u es by he linea combina ion o spec a o pu e
2 e e ence s anda ds [34,35]. The p ocess consis s o wo s eps. In he i s one, he
3so wa e uses a sum o Gaussian and/o Lo en zian band p o iles and a leas -squa e
4 i ing o p oduce o each e e ence compound (in his wo k akaganei e, lepidoc oci e,
5goe hi e and magne i e) a calcula ed spec um ha i s he eco ded expe imen al one
6[36]. The calcula ions and he i ing p ocedu es pe o med by PALME so wa e ha e
7been de ailed in a speci ic publica ion [37].
8In a second s ep, a linea combina ion o he calcula ed s anda d spec a is used o he
9 i ing o a spec um simila o he sample spec um by means o he leas -squa es
10 c i e ion and he Le enbe g-Ma qua d algo i hm. A e alida ion o he i ing by he
11 use , PALME so wa e p o ides a x documen including he con ibu ion o each
12 s anda d (exp essed as a weigh ing coe icien ) o he decomposi ion o he sample
13 spec um.
14 2.4 Co osion sys em s abili y e alua ion
15 A e comple ing he semi-quan i ica ion o he i on phases, he pe cen age alues o
16 each compound we e used o de e mine he sample co osion s abili y.
17 As explained abo e, he adjus ed index (*PAI index) conside s he p esence o
18 akaganei e, lepidoc oci e as eac i e phases; and goe hi e, and magne i e as p o ec i e
19 ones (Equa ion 1). Unlike Yamashi a e al. [30], due o i s passi i y and s abili y,
20 magne i e (Fe3O4) is he e conside ed as p o ec i e.
21 In his ligh , he s abili y o a chaeological co osion samples was calcula ed as ollows:
22 (Eq.1)
Co osion s abili y
=
mass ac ion
(
α
FeO(OH)
)
+
(Fe
3
O
4
)
mass ac ion
(
γ
FeO(OH)
)
+
(
β
FeO(OH))
23 In he case o he mix u es o s anda ds, he eliabili y o he s abili y calcula ion was
24 de e mined by compa ison wi h he esul s ob ained using he weigh ed p opo ions o
25 each compounds. In he case o a chaeological samples, he eliabili y e alua ion was
26 pe o med using as a e e ence he alue calcula ed h ough he semi-quan i ica ion
27 alues ob ained by X- ay di ac ion (XRD) analysis.
28 2.5 X- ay di ac ion
8
1In o de o cha ac e ize and semi-quan i y he i on phases in he a chaeological us
2samples, a PRO PANaly ical Xpe XRD was used.
3The sys em is equipped wi h a coppe ube, a e ical goniome e (B agg-B en ano
4geome y), a p og ammable di e gence sli , a seconda y g aphi e monoch oma o and a
5Pixcel de ec o . The condi ion o all measu emen s we e se a 40 KV, 40 mA and a
6scan anging be ween 5 and 70º 2 he a.
7I is impo an o ecall ha he peaks’ shape o he XRD di ac og am depends on he
8c ys allini y o he phases ( he na owness o he peaks inc ease wi h inc easing sho
9and long ange o de ing). Fo his eason semi-quan i a i e alues we e ob ained by
10 ea ing a eas alues.
11 To ob ain semi-quan i a i e da a om he collec ed di ac og ams, wo di e en
12 so wa es we e used. Bo h Xpe HighSco e and EVA so wa e (PANanaly ical,
13 Holland) apply he Re e ence In ensi y Ra io (RIR) me hod o p edic he phase
14 abundances. Conside ing ha he in ensi y o a di ac ion peak p o ile is a con olu ion
15 o many ac o s, he RIR me hod measu es and educes o a cons an all he ac o s
16 excep concen a ion o de e mine phases concen a ion (by compa ison o a e e ence
17 pa e n). Al hough he so wa es a e bo h based on he Re e ence In ensi y Ra io
18 me hod, he algo i hm used o he decomposi ion o he expe imen al da a is di e en ,
19 which can esul in di e en semi-quan i a i e esul s.
20 3 Resul s and Discussion
21 3.1 Cha ac e iza ion o pu e s anda ds
22 The semi-quan i ica ion pe o med by PALME so wa e is based on he decomposi ion
23 o he ib a ional spec um o a sample by compa ison wi h pu e e e ence spec a.
24 Thus, he i s s ep was ocused on he collec ion o he cha ac e is ic FTIR spec a o
25 pu e akaganei e, lepidoc oci e, goe hi e and magne i e using he same expe imen al
26 condi ions in o de o ob ain abso bances ( ela i e in ensi ies be ween bands) ela ed o
27 each sample speci ici ies, spec ome e cha ac e is ics and measu emen mode
28 ( ansmi ance, DRIFT, ATR). Fo example, Figu e 1 epo s he FTIR spec a o pu e
29 i on phases, collec ed by using he JASCO 6300 labo a o y sys em in ansmi ance
30 mode.
9
1
2Figu e 1. FTIR aw spec a o i on oxide s anda ds ca ied ou using he Jasco 6300
3sys em in ansmi ance mode.
4As showed in Figu e 1, he magne i e ib a ional spec um was cha ac e ized by he
5p esence o s ong signals a 588 and 3437 cm-1 (Figu e 1a). Goe hi e spec um showed
6 h ee s ong peaks a 615, 798 and 905 cm-1 espec i ely, oge he wi h wo b oad bands
7a 3136 and 3431 cm-1(Figu e 1b). Lepidoc oci e spec um s ood ou by he p esence o
8a main peak a 1023 cm-1, ollowed by se e al seconda y signals a 485, 615, 759, 1152,
93014 and 3414 cm-1(Figu e 1c). Finally, akaganei e s anda d p o ided an in ense double
10 peak a 648 and 693 cm-1, oge he wi h wo weak signals a 844 and 1623 cm-1 and a
11 b oad band a 3385 cm-1 (Figu e 1d).
12 To illus a e he signal di e ences p oduced by each acquisi ion mode, he compa ison
13 o he akaganei e spec a eco ded using he Jasco 6300 in ATR, DRIFT and
14 ansmi ance modes a e shown in Figu e 2.
15
16 Figu e 2. Compa ison among akaganei e spec a ob ained using he Jasco 6300 sys em
17 in ATR, DRIFT and ansmi ance modes.
18 As e idenced in Figu e 2, ansmi ance and DRIFT modes we e mo e sensi i e o he
19 O-H bonds ib a ions wi h espec o he ATR mode [38,39], p omo ing he
20 enhancemen o he hyd oxide signals on he spec um o pu e akaganei e (3385 and
21 3470 cm-1). This is due o he lesse pene a ion o he high wa enumbe IR ligh s in
22 ATR mode which esul in a smalle olume sampled and hen a lowe abso bance. As
23 he e he ATR spec a we e no co ec ed by he ATR co ec ion unc ion which is
24 commonly p o ided by he IR so wa e (we choose o no in oduce such co ec ions o
25 spec a) he di e ences be ween he ATR p o ile and he ansmi ance/DRIFT ones
26 emain. Fu he mo e, i mus be poin ed ou ha , using he DRIFT me hod, he in a ed
27 adia ion pene a es he sample/KB mix u e, p oducing a high numbe o e ac ions
28 and abso p ion p ocesses which esul in an enhancemen o he in ensi y in he
29 in e aces con ibu ion, and combina ion bands [40]. This s a emen was con i med by
30 expe imen al da a owing o he p esence o se e al seconda y peaks in a wa eleng h
16
1Sample 3) equi e speci ic s abiliza ion ea men s (such as desalina ion ba hs) ha
2minimize pos -exca a ion deg ada ion issues.
34 Conclusions
4This pape in oduces a new analy ical me hod, based on he use o FTIR spec oscopy,
5 o e alua e he s abili y o a chaeological a e ac s co osion sys ems.
6In he i s s ep, he semi-quan i ica ion o s anda d mix u es spec a collec ed by means
7o labo a o y sys em (Jasco 6300) indica ed ha he mos eliable esul s we e p o ided
8as expec ed by he decomposi ion o ansmi ance spec a (powde dispe sed in a KB
9pelle ). This wo k also demons a ed ha , by pe o ming spec a ea men s ( inge p in
10 egion selec ion and baseline co ec ion), he me hod accu acy especially o hose using
11 DRIFT o ATR p ocedu es can be signi ican ly imp o ed.
12 A e wa ds, he esul s ob ained by means o labo a o y sys ems (T ansmission, DRIFT
13 & ATR) we e compa ed o hose o he po able Alpha IR spec ome e in ATR mode.
14 As p o ed by he end line showed in Figu e 4, he esul s ob ained by semi-
15 quan i ying ea ed Alpha spec a we e good enough o enable he applica ion o he
16 p oposed p o ocol also o on si e analysis. Once he analy ical p ocedu e was alida ed,
17 he cu en a ailabili y o a ious small mo able ATR-FTIR de ices allows wo king ou
18 o analy ical labo a o ies, in es o a ion wo kshops, museums o e en on he
19 a chaeological ield.
20 PALME concen a ion alues ob ained by he decomposi ion o bo h po able (in ATR
21 mode) and labo a o y (in ansmi ance mode) spec a we e used o calcula e he
22 s abili y alues o bo h s anda d mix u es and a chaeological samples. Conc e ely, he
23 expe imen al s abili y alues ob ained om a chaeological i on co osion samples we e
24 in line wi h hose calcula ed om XRD da a. Fo his eason we belie e ha he FTIR-
25 PALME me hod ep esen s a iable al e na i e o hose based on he ea men o X-
26 Ray di ac og ams o bo h i on phases semi-quan i ica ion and s abili y e alua ion.
27 Finally, i mus be emphasized ha FTIR analyses equi e a smalle amoun o sample
28 (0.3 - 0.5 mg in ansmi ance mode) compa ed o he XRD echnique. Thus, his
29 me hod can be pa icula ly sui able o he s udy o i on-based objec s o cul u al
17
1in e es because he amoun o sample ha is usually a ailable is e y li le due o he
2special cha ac e is ic o he cul u al objec s.
3In conclusion, he eliabili y o he p oposed me hod o PAI index de e mina ions could
4 ep esen a g ea ad an age o conse a o s, helping hem on p edic ing he co osion
5beha iou o i on a e ac s and consequen ly planning op imal conse a ion ea men .
6Acknowledgmen s
7This p ojec has been unded by he UFI "Global Change and He i age" p ojec (Re
8UFI 11-26 UPV-EHU), he DISILICA-1930 p ojec ( e BIA2014-59124) and he
9Eu opean Regional De elopmen Fund (FEDER). Ma co Vene anda hanks he
10 Minis y o Inno a ion and Compe i i eness (MINECO) o his p e-doc o al ellowship.
11 We would like o hank he LAPA labo a o y o p o iding i on phases s anda ds and
12 P o esso Juan Manuel Gu ie ez Zo illa o his suppo in he syn hesis o akaganei e.
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Highligh s:
A new i on co osion semi-quan i ica ion me hod is p oposed.
A homemade decomposi ion so wa e (PALME) was used o he ea men o
Fou ie T ans o m In a ed Spec oscopy (FTIR) spec a.
This app oach was applied o he s udy o bo h, mix u es o pu e i on co osion
s anda ds and eal a chaeological co osion samples
Fas , eliable and epe i i e esul s we e eached using ex emely small quan i y
o ma e ial (below 0.5g).
